TW201209143A - Flame-retardant containing a cyclic amine salt and flame-retardant resin composition - Google Patents

Abstract

The present invention provides a halogen-free flame retardant for resins which exhibits excellent flame retardancy and has reduced problems relating to moisture resistance and blooming. The present invention relates to a flame retardant containing a cyclic amine salt having a specific chemical structure, and to a flame retardant resin composition comprising the flame retardant and a resin component, wherein the amount of the cyclic amine salt is 1 to 100 parts by weight relative to 100 parts by weight of the resin component.

Description

201209143 VI. INSTRUCTIONS OF THE INVENTION: I: TECHNICAL FIELD OF THE INVENTION The invention relates to a novel flame retardant and a flame retardant resin composition. In particular, it relates to a flame retardant containing a cyclic amine salt, a flame retardant resin composition containing the flame retardant, and a molded article thereof. More specifically, it is useful for forming a molded article and an extruded article, and is suitable as a non-halogen flame retardant having little environmental load such as a home electric appliance, an OA machine, an automobile part, or a wire coating material. Synthetic resin composition and molded article.

L·J Background of the Invention = Polyolefin resin, polystyrene resin, polyacrylic resin, polyester resin, polyether resin, polycarbonate resin, etc. A thermosetting resin such as a resin or an epoxy resin, or a resin alloy obtained by such a combination, is widely used in accordance with characteristics of each of its unique mechanical properties, thermal properties, and moldability. For example, building materials, electrical machinery materials, vehicle parts, automotive interior parts, household goods and various other industrial supplies. However, since these synthetic resins generally have the disadvantage of being easily burned, many proposals have revealed various methods for flame-retarding synthetic resins. A general flame retarding method for synthetic resins is a method in which a flame retardant is formulated in a resin. Among the methods conventionally used for flame retardation, the most commonly used examples are methods of adding cerium oxide and a functional organic compound. As the organic compound, there are 201209143 bisdibromopropyl ether of tetrabromobisphenol A, hexabromocyclododecane and tetrabromobisphenol A, and didibromopropyl ether of tetrabromobisphenol S. , 2,3-dibromopropyl iso-isocyanate, bistribromophenoxyethane, hexabromobenzene, decabromobiphenyl ether, ten desert biphenyl bromide, and the like. However, in consideration of the worldwide environmental problems in recent years, ii-based organic compounds which are likely to generate harmful gases (hydrogen bromide) during combustion are strongly demanded when they are used. Therefore, there have been several proposals for a method of imparting flame retardancy to a synthetic resin without using a halogen-based flame retardant. One of them is a method of adding an inorganic hydroxide such as aluminum oxide or magnesium hydroxide. However, since the inorganic hydroxide exhibits flame retardancy by water generated by thermal decomposition, the flame retardancy cannot be exhibited unless it is added in a large amount. Because of such a large amount of addition, there is a problem that the original functions of the resin such as workability and mechanical properties are remarkably lowered. As another method of not using a halogen-based flame retardant, there is a method of using an organic phosphorus compound such as triphenyl phosphate or tridecyl phenyl phosphate. However, this organophosphorus compound is a phosphate-type flame retardant, and when a synthetic resin such as polyester is heated and kneaded at a high temperature, a transesterification reaction occurs, and the molecular weight of the synthetic resin is remarkably lowered, and as a result, the synthesis is impaired. The original physical properties of the resin. Further, the phosphate-based flame retardant itself may be slowly hydrolyzed by moisture in the air to form phosphoric acid, and when phosphoric acid is formed in the synthetic resin, the molecular weight of the synthetic resin may be lowered or used for electrical purposes. • There is a risk of short-circuiting when using electronic parts. On the other hand, as a non-halogen flame retardant, there have been many proposals for the use of phosphates including ammonium polyphosphate. However, when such a phosphate is added in a large amount, the phosphate is low in flame retardancy and poor in moisture resistance, so that the appearance of the surface product, mechanical properties, and the like are significantly lowered in the molding 4 201209143. Further, when a resin molded article composed of the flame retardant composition is used at (four) degrees, the bleeding of the phosphate phenomenon caused by the blooming phenomenon causes a lot of fatal defects. In order to improve the above-mentioned shortcomings, there is also a proposal to disclose a coated polyphosphoric acid, which is made of a modified and resistant trimeric amine crosslinked type, a benzene crosslinked type, an epoxy crosslinked type or a (tetra) coupling agent and a The surface of the cross-linked polyethylene glycol cross-linking type is "formed. However, the compatibility or dispersibility of the side-side fat is poor, and there is a problem that high mechanical strength cannot be obtained. Further, it will contain many coated ammonium polyphosphates. When the resin composition is kneaded, the coating is destroyed by heat and stress, and the same problem as described above (a problem such as bleeding due to moisture absorption) is likely to occur. Usually, since the resin composition containing ammonium polyphosphate is When the kneading occurs, the thermal decomposition occurs from about 200 C. Therefore, the thermal decomposition product is also mixed in the kneading and the water is wetted in the strands, so that the physical properties and productivity of the flame retardant resin composition are changed. For example, it has been proposed in the prior art to disclose a multi-acid D-dysin salt or the like (Patent Documents 1 to 4). However, even with these conventional techniques, there are still the same problems as described above, and there are many practical applications. The problem should be improved. In other words, since condensed phosphate salts such as ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate are basically water-soluble or water-absorbent, these additions are heat resistance and moisture resistance of the resin composition. In order to improve the situation, there are proposals to disclose organic salts of aliphatic amine salts such as aromatic phosphoric acid esters (Patent Documents 5 to 7). However, although aromatic phosphorus 5 201209143, it has the following chemical formula. (1) - The aliphatic amine salt of hydrazine has a predetermined flame retardancy and a water-absorbent organic salt which is highly water-absorptive. For example, the salt of the Wei-Phenylbenzene (4) is in accordance with the salt. ]

The substance is an anion component, that is, dihydrogen phosphate and ionization: a rust salt in which the component, that is, t-tether, is alternately coordinated, because it is highly water-soluble and insoluble in most organic solvents, and the resin is compatible. Very bad. Therefore, when the phosphoric acid-tolyl group has a low heat resistance and is kneaded as a resin composition, it is thermally decomposed at a kneading temperature of 18 〇 to 2 〇〇〇c, and a large amount of highly toxic pair is generated. The fatal disadvantage of indophenol gas is not practically achievable. [Patent Document 1] Japanese Patent Laid-Open No. 2000-169731 [Patent Document 2] Japanese Patent Laid-Open No. 2003-026935 [Patent Document 3] WO2004-000973 [Patent Document 4] WO2010-013400 [Patent Document 5] PCT Patent Laid-Open No. 2001-064453 [Patent Document 6] Japanese Patent Laid-Open No. 2001-288309 6 201209143 t Patent Document 7] Japanese Patent Special Opening 2 〇 8〇 633 [Intra-Solution] Summary of Invention The subject of the present invention is to provide a flame retardant which imparts excellent flame retardancy by eliminating various problems of the prior art, and provides a flame retardant resin composition containing a composition and forming thereof. Formed into a molded product. In order to achieve the above object, the inventors of the present invention have found that the above object can be achieved by using a cyclic amine salt of a specific aromatic phosphate as an active ingredient of a flame retardant. The invention has been made. That is, the present invention relates in particular to a flame retardant and a flame retardant resin composition containing the cyclic amine salt described below. A flame retardant composition containing a cyclic amine salt, which comprises a cyclic amine salt of an aromatic acid-sodium salt, wherein the aromatic amine-Ss-like amine salt is derived from 1) An aromatic phosphodiester of an anion component and 2) a cyclic amine which is a cationic component, wherein the cyclic amine salt is represented by the following formula (1), [Chemical 2]

[wherein, Ri to R1 () are the same or different from each other and represent a halogen atom or a hydrocarbon group which may have a substituent. A is a cyclic amine in which at least one imine group (-ΝΗ·) is cyclically bonded to an alkyl group of 201209143. The γ system represents an imido group. The z system represents an oxygen atom, a sulfur atom or an imine group. The n system represents an integer of 1 to 10. The m system represents an integer of 0 to 9. 1 is an integer of 1 to 10]. 2. The flame retardant composition according to Item 1, wherein the cyclic amine salt of the aromatic phosphodiester is represented by the following component (II) and the following formula (III); The composition ratio of the component B indicated is that the ion equivalent ratio is A component/B component = 0.8/1.0 to ι 〇 /1 2 , wherein, the general formula (II): [Chemical 3]

[wherein, they are the same or different from each other and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; Formula (III): [Chemical 4]

[In the formula, A represents a cyclic amine in which at least one imine group (-NH-) is bonded to a stretching group to form a cyclic amine. Y represents an imine group. The Z system represents an oxygen atom, a sulfur atom or an imine group. The m system represents an integer of 0 to 9]. 3. The flame retardant composition of the above item 1 wherein the content of the aromatic phosphate monoester 8 201209143 is 1% by weight or less of the flame retardant composition. 4. The flame retardant composition according to the above item 1, which further contains at least one of phosphates. A flame retardant resin composition containing the flame retardant composition and the resin component according to the above item 1, wherein the aromatic phosphoric acid is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the resin component. A cyclic amine salt of a diester. A flame retardant resin composition containing the flame retardant composition and the resin component according to the above item 4, wherein the aromatic phosphoric acid is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the resin component. a cyclic amine salt of a diester, and 1 to 50 parts by weight of the phosphate. 7. The flame-retardant resin composition according to the above item 5 or 6, wherein the resin is a polyolefin-based resin. 8. A flame-retardant resin molded article obtained by molding the flame-retardant resin composition according to any one of items 5 to 7. 9. The flame-retardant resin molded article according to Item 8, which is used in electrical/electronic parts, OA machine parts, home electric machine parts, automobile parts, or machine parts. 10. A method for producing a cyclic amine salt of an aromatic phosphodiester, which is a cyclic amine salt of an aromatic phosphodiester represented by the following formula (1);

201209143 [wherein, RcRio is the same or different from each other and represents a hydrogen atom or a hydrocarbon group which may have a substituent. A is a cyclic amine in which at least one imine group (-NH-) is cyclically bonded to an alkylene group. The Y system represents an imido group. The Z system represents an oxygen atom, a sulfur atom or an imine group. The η system represents an integer of 1 to 10. The m system represents an integer of 0 to 9. 1 is an integer of 1 to 10], and the production method comprises the following steps: (1) reacting a compound represented by the following formula (IV) with a hydroxyphosphorus phosphate in the presence of an amine; 6]

^4^5 [wherein, Ri-Rs are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent], and a halogen-containing aromatic phosphate acid represented by the following formula (V) is synthesized. The step of the derivative, [Chemistry 7]

[wherein, Ri-Rio are the same or different from each other and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; (2) by hydrolyzing the elemental aromatic phosphate acid derivative, 10201209143 a step of an aromatic phosphodiester represented by the following formula (II), [Chemical 8]

(II) wherein RfRnj is the same or different and represents a hydrogen atom or a hydrocarbon group which may have a substituent; and (3) by adding the following formula (VI) to the aromatic phosphodiester a step of synthesizing the compound represented by the above formula (I), wherein the compound is represented, [Chemical 9]

[In the formula, A represents a cyclic amine in which at least one imine group (-NH-) is bonded to an alkyl group to form a ring. The Y system represents an imido group. The Z system represents an oxygen atom, a sulfur atom or an imine group. The m system represents an integer of 0 to 9]. EFFECTS OF THE INVENTION Since the flame retardant of the present invention contains a cyclic amine salt having a specific chemical structure, it is possible to exhibit more excellent flame retardancy than the prior flame retardant. Therefore, even if a relatively small amount is added, the required flame retardancy can be exhibited. In other words, it is possible to effectively maintain the original properties of the material (resin or the like) to be added, and to impart excellent flame retardancy. Further, since the flame retardant of the present invention is excellent in moisture resistance, it is possible to effectively prevent or prevent problems such as bleeding due to moisture absorption, blooming, and the like, and the problem of low flame retardancy due to bleeding or the like. Further, since the cyclic amine salt of the active ingredient of the flame retardant of the present invention does not contain a halogen element in the molecule, the generation of harmful gas can be effectively suppressed even when the flame retardant resin and the molded article are burned. In particular, when the present invention is applied as a flame retardant such as a polyolefin-based resin, it is possible to exhibit excellent flame retardancy with a less-added amount of a flame retardant by using a sulphate in combination with the above-mentioned cyclic amine salt. Conventionally, the acid salt of a polyphosphate or the like is water-soluble or highly water-absorptive. Therefore, the flame retardant resin composition and the molded article contained in the flame retardant are not effective in suppressing mold deposition and bleeding (or blooming) of the flame retardant. In the flame-retardant resin composition and the molded article containing the flame retardant of the present invention, the polyphosphates can be highly compatible with the resin while maintaining the physical properties of the various resins. It is possible to effectively suppress the mold deposition and bleed (or bloom) of the polyphosphate, and to impart a high flame retardancy equivalent to or higher than that of the prior art to the polyolefin resin. Thus, the flame retardant of the present invention can be suitably used, for example, as a flame retardant for use in a material containing an organic component. In particular, a flame retardant which is added as a composition containing a resin component (for example, a composition containing a resin component of 50% by weight or more) can be suitably used. [Embodiment] Hereinafter, a flame retardant composition containing a cyclic amine salt as a main component and a flame retardant tree 12 to be blended in a resin component of the present invention will be described in detail. A composition and a molded article obtained by molding the composition. 1. A flame retardant composition containing a cyclic amine salt (1) a cyclic amine salt and a synthetic method thereof (1-1) a cyclic amine salt The flame retardant for a resin of the present invention contains 1) an anionic component, that is, A flame retardant of a cyclic amine salt of an aromatic phosphodiester composed of an aromatic phosphodiester and 2) a cationic component, that is, a cyclic amine, wherein the cyclic amine salt of the aromatic phosphodiester is contained a cyclic amine salt of an aromatic phosphodiester represented by the following formula (1), [Chem. 10]

[wherein, RpRio is the same or different from each other and represents a hydrogen atom or a hydrocarbon group which may have a substituent. A is a cyclic amine in which at least one imine group (_nh_) is cyclically bonded to an alkylene group. The γ system represents an imine group, and the Z system represents an oxygen atom, a sulfur atom or an imine group. The η system represents an integer of 1 to 1 。. The m system represents an integer of 0 to 9. 1 is an integer of 1 to 1 ]]. In other words, the aromatic phosphodiester cyclic amine salt represented by the following formula (I) (hereinafter also referred to as "the cyclic amine salt of the present invention") functions as an active ingredient of the flame retardant of the present invention. . The flame retardant of the present invention contains hydrazine or two or more kinds of cyclic amine salts of the present invention. The cyclic amine salt of the present invention contains an aromatic phosphodiester as an anion 13 201209143 subcomponent (component A) and a cationic component (component B) which is composed of a cyclic amine. Such a cyclic amine salt can be used as known or commercially available. Hereinafter, the component A and the component B will be described separately for the cyclic amine salt of the present invention. In the cyclic amine salt of the present invention, the aromatic phosphoric acid dimer of the component A is represented by the following formula (II).

[wherein RpRw are the same or different from each other and represent a hydrogen atom or a hydrocarbon group which may have a substituent]. Ri to Ri in the formula (11) represents a hydrogen atom or a substituent which may have a substituent. Further, the respective r, -r1q groups may be the same substituents or may be mutually different substituents. Particularly from the viewpoint of economy, in the present invention, the r-Riq is preferably a hydrogen atom as compared with a hydrocarbon group which may have a substituent. The hydrocarbon group is not particularly limited, and may be a chain (any of a straight chain or a branched chain) or a ring (any one of a condensed polycyclic ring, a crosslinked ring, or a spiro ring). Any of them may be, for example, a cyclic hydrocarbon group having a side chain, a fluorenyl saturated hydrocarbon group or an unsaturated hydrocarbon group. The term "sodium group" may, for example, be a (tetra) group, a cyclofilament, a (tetra) group, an aryl group, a '. The total carbon number of the nicotine groups (the number of carbon atoms having a substituent in the case of a substituent) is not limited, and it is usually applied to the right, and is preferably about 14 201209143 1 to 4. More specifically, a fluorenyl group, an ethyl group, a propyl group, a butyl group, an ethylene group or the like can be exemplified. Further, a substituent may be introduced into the radical. The substituent may, for example, be a benzyl group, an anthracene group, an anthrace group, a cyano group, a aryl group, a sulfhydryl group, a fluorenyl group, a carboxylic acid group or a thioether group. Among these, as a preferable specific example, Ri'R3, R5, R6, Rs A atom or fluorenyl group, and r4, r7 and r9 are a hydrogen atom. More specific examples of the aromatic phosphodiester represented by the formula (I) include compounds represented by the following formulas (1) to (7). The compounds themselves are also available for use on a well-known or commercial basis. [化 12]

(3) Component B Among the cyclic amine salts of the present invention, the cyclic amine constituting the component B is represented by the following formula (III). 15 201209143 [Chem. 13]

(III) [A represents a cyclic amine in which at least one imine group (·ΝΗ-) is cyclically bonded to at least an alkylene group. The γ system represents an imido group. 2 represents an oxygen atom 'sulfur atom or an imine group. The m system represents an integer of 〇~9. ]. The above-mentioned A is a cyclic amine in which at least one imine group (-NH-) is cyclically bonded to an alkyl group. Therefore, when m = 0, the Z system becomes an amine group. When m=0, for example, a bite, a ratio of 11 to pyrrolidine, etc. is met. As the alkylene group, for example, an anthracene group, an exoethyl group, a propyl group, a butyl group or the like can be used. In the present invention, an alkylene group having a total carbon number of 2 to 6 is particularly preferred. As the cyclic amine, for example, one or more imine groups (-NH-) can be used, and a compound which is cyclically bonded by an oxygen atom, a sulfur atom or an imine group and a stretching group can be used. More preferably, a cyclic amine in which two or more imine groups are cyclically bonded through an alkyl group is more preferable. Specific examples of the cyclic amine include aziridine, azetidine, pyrrolidine, piperidine, azepane, and arsenic nitrogen. Azocane, azonane, azecane, diazetidine, mouth rice, sitting, bite, brigade, morpholine, Thiomorpholine, 1,4,7-triazaindole, 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13-pentanitro Heterocyclic pentadecane, 1,4,7,10,13,16-hexazacyclooctane, etc. In the present invention, the cyclic amine A can be appropriately selected from cyclic amines or cyclic polyamines. Examples of the cyclic amines include a ratio of σ to each of σ. Rice bites, licks, and travels. Well, hollyin, thiophene, etc. Further, examples of the cyclic polyamines include a cyclic polyamine in which two or more of a combination of an imido group (-ΝΗ-) and an ethylidene group (-CH2-CH2-) are cyclically bonded. class. Among these, in particular, from the viewpoint of being inexpensive and easy to obtain, piper cultivation is the best. Specific examples of the cyclic amine represented by the formula (III) include compounds represented by the following formulas (6) to (10). [Chem. 14]

(9) (10) The cyclic amine salt of the present invention can be suitably used when kneading with a resin component or when heat resistance is high during molding. Therefore, the cyclic amine A is the same as the first amine. 2 amine or 3 amine is preferred. Further, from the flashing of the pyrolysis gas which may occur during molding, the cyclic amine can be more suitably used than the aliphatic amine having low heat resistance. The composition ratio of the A component to the B component of the cyclic amine salt of the present invention is not particularly limited, and in order to more effectively maintain flame retardancy, moisture resistance, and the like, the A component 17 201209143 and the B component have respective ion equivalents. Equality is preferred. By the fact that the respective ion equivalents are equal to each other, the content of the remaining ionic components can be reduced, and as a result, the appearance of water solubility or hygroscopicity can be suppressed or prevented, and the appearance of the molded article or the like caused by the film can be prevented from being lowered, and the physical properties are lowered. Wait. From such a viewpoint, when the composition ratio (ion equivalent ratio) of the A component and the B component of the cyclic amine salt of the present invention is in the range of A component/B component = 〇·8/1 〇 丨〇 丨〇 /1 2 ' It does not cause the aforementioned defects and is more suitable for use as a flame retardant. Further, in the present invention, it is preferable that the composition of the sputum component and the thief are divided into eight equal amounts. i Preferred Embodiment of the Cyclic Amine Salt of the Present Invention The flame-retardant resin composition of the present invention and its molding. The task of the cyclic amine salt of the present invention, as a function of the flame retardant, of course, can also exhibit various types of work shovel such as an anti-hygroscopic agent and an anti-blooming agent. In view of the above, in the case of exemplifying a more preferred cyclic amine salt of the present invention, in the case of selecting a pyridine as a preferred example of the component B, the bovine aj can be represented by the following formulas (11) to (16). Compound. 201209143 [化15]

Further, the A component which constitutes the cyclic amine salt of the present invention, that is, the aromatic phosphodiester and the component B, that is, the cyclic amine, may be used. Further, it is also possible to use a ring of the aromatic acid dish of the aromatic acid obtained by a method known to the public. (1-2) Method for synthesizing cyclic amine salt of the present invention Although the cyclic amine salt of the present invention can be produced by a known method, it is particularly preferable to produce it by the production method according to the present invention. A well-known method for synthesizing an aromatic phosphate acid derivative represented by the general formula (π) from a compound represented by the general formula (IV) is known as a dish and a compound thereof, Volume 2 Phosphorus and its compounds Volume 1961 , Interscience Pubublishers, Inc., New York, 1230 - Method of recording, that is, a manufacturing method by partial hydrolysis from the use of citrate triester; and production of monoalkyl dihydroxy phosphate and hydroxy phosphate After the mixture of the dialkyl esters, a production method of selective distribution and the like are carried out by using the difference in water solubility. When the synthesis route of the above-mentioned publication is applied, an aromatic mono-salt ester or an aromatic di-disc ester can be synthesized by reacting an excess of the compound represented by the above formula (IV) with phosphorus pentoxide or hydroxyphosphoric acid phosphorus. And a mixture of aromatic triphosphates. However, because this method is low in productivity and labor-intensive, it is not an economically advantageous method. For example, when hydroxyphosphoric acid is used for the phosphorylation of benzene, a large amount of excess hydroxyphosphorus is added to preferentially synthesize a monophenyl phosphate (monoester), and Adding 3 equivalents of benzene to carry out the reaction's ability to preferentially synthesize the disc acid (triester). However, even if the synthetic route of the above-mentioned publication is used, it is difficult to directly select a direct synthesis of mono-diphenyl vinegar (diester). In contrast, the production method of the present invention is a method in which a compound represented by the formula (IV) is reacted with a hydroxyhalide halide in the presence of an amine, and a compound represented by the formula (i) is produced via a compound of the formula (V) 201209143. The synthetic route of the cyclic amine salt. According to the production method of the present invention, the target compound can be directly obtained in a one pot at a better yield. More specifically, since it is not necessary to carry out the separation and formation steps of the intermediate product in the respective processes of the synthesis of the target compound, that is, the cyclic amine salt of the present invention, it is possible to continuously transfer to the next process without occurrence. As the yield of the intermediate purification is lowered, a high yield can be obtained, and since the manufacturing cost can be reduced by simplification of the steps, it is also an economically excellent method. From such a viewpoint, in the production of the cyclic amine salt of the present invention, it is preferred to use the production method of the present invention. The production method of the present invention comprises the production method of the following steps: (1) reacting a compound represented by the following chemical formula (IV) with a hydroxyhalide halide in the presence of an amine, [Chem. 16]

[Formula, wherein R1 to R_5 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent], and a step of synthesizing a halogen-containing aromatic phosphate acid derivative represented by the following formula (V) (A step), [Chem. 17] 21 (V) 201209143

[wherein, Ri~Ri〇 are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; (2) The following synthesis is synthesized by hydrolyzing the halogen-containing aromatic phosphate acid derivative; Step of the aromatic phosphodiester represented by the formula (II) (step B), [Chem. 18]

[wherein, Ri to Rio are the same or different from each other and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; and (3) by adding the following formula to the aromatic phosphodiester in an organic solvent ( a step of synthesizing the compound represented by the above formula (I) by a compound represented by VI) (step C), [Chem. 19]

(III) In the formula, A represents a cyclic amine in which at least one imine group (-NH-) is bonded to an alkyl group to form a ring. The Y system represents an imido group. The Z system represents an oxygenogen 22 201209143 subunit, a sulfur atom or an imine group. The m system represents an integer of 〇~9]. In the step A, the above formula (V) is synthesized by adding an amine to a reaction system containing a hydroxyhalogenated phosphorus and a phenol derivative represented by the above formula (Iv) to dehydrogenate the hydrogen. A halogen-containing aromatic phosphate acid derivative represented by the same. The amine added at this time functions as a catalyst for efficiently promoting the above selective vinegar reaction. The compound represented by the formula (IV) can be reacted by using a commercially available cumbersome and base-based filling as a raw material. As the radical-based disk, for example, hydroxy-hydrogenated phosphorus, hydroxyphosphonium bromide or the like can be used. When a hydroxy group is used to vaporize phosphorus, the halogen atom represented by the formula (V) is a gas. Further, when phosphorus hydroxybromide is used instead of the hydroxyl group, the halogen atom represented by the formula (V) is bromine. Further, as a catalyst for efficiently promoting the above selective esterification reaction, it is allowed to coexist with an amine in a reaction system. The type of the amine is not particularly limited, and examples thereof include triethylamine, pyridine 'N,N-dimethylaniline, 1,8-diazabicyclo[5_4 4.]·7-undecene, and 1, At least one of diazabicyclo[4.3.0]-5-pinene or 4-diaminopyridine. Among them, from the economic point of view, triethylamine is preferred. As a method of synthesizing the compound represented by the general formula (V), for example, the hydroxy derivative is mixed with the phenol derivative represented by the general formula (IV), and is mixed at a normal temperature (about 10 to 40 ° C). The amine of the hydrogen halide catalyst can be used. Since the reaction rate is low when the reaction temperature is lower than 10 C, the reaction time is increased. Further, when the reaction temperature exceeds 40 C, the reaction is out of control and a by-product such as a diester body is formed in addition to the bidentate body represented by the formula (v), resulting in a low reaction yield of 23 201209143. The mixing ratio of each raw material is 4 to G.6 m with respect to the benzene derivative of the formula ι ν.丨About: 〇.45~〇.55_ can be around. In addition, the general sense of the entanglement of the 纠 耳 骑 生物 生物 生物 生物 生物 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑 骑The addition ratio of the raw material is outside the above range. One or three (four)^ possibilities other than the two (four) represented by the general formula (v). The above-mentioned reaction is preferably carried out in a solvent, because the (IV) gas salt which will form an amine is preferred. As a solvent, for example, a flue-based solvent such as benzene'toluene or hexanone can be suitably used. Second, a solvent such as a ketone or a bismuth, or an aprotic organic solvent such as a solvent such as a gas or a gas. Wait.匕蛵In view of the above solvent, in order to solution the aqueous solution of the amine i-hydrogen salt, the eight layers are formed, and the second form of the general formula (V) is _ (the organic solvent is dissolved in the presence of 余). It is necessary to avoid the nuclear (4) solution. Therefore, in order to carry out the continuous reaction, the water is preferably used in the form of a water-soluble light solvent (a solvent having a specific gravity lower than water). The aroma-acid s is preferably carried out continuously in the same reaction tank. In order to stratify the drawn emulsion of the amine produced as a by-product of the above reaction, as described above, the formula (V) The diacetate (existing in the organic (four) layer towel) is subjected to thorough extraction, and it is preferable to use 人X human water in the % system by charging it below normal temperature ((9). C or less). 201209143 i is then placed and separated into an organic solvent layer and an aqueous layer, and then the aqueous layer is removed to remove the amine hydrogen salt from the reaction system. At this time, the temperature is above normal temperature (temperature exceeding 4 叱) It is considered that although a little 疋, the genus of the formula (V), the singularity of the saponin, and the formation of the acid of the formula (F) The second g body, although it is a little, but because it will move from the organic solvent to the water layer, its silk has a reduced yield. In the manufacturing method of the present invention, especially in the A step, in order to obtain the crucible, The aromatic acid-acid represented by the formula (II) is a derivative of the desired product represented by the formula (IV), and the addition ratio of the base cartridge is about eq. About G. 5 equivalents, because it can be synthesized stoichiometrically without loss, is economically very advantageous. Step B is in step B by synthesizing aromatics by hydrolyzing a dentate-containing aromatic phosphate acid derivative. A phosphodiester, that is, an aromatic dish diester represented by the formula (11), which is obtained from the dentate-containing aromatic phosphate acid derivative (aromatically functional phosphodiester) represented by the formula (v) The hydrolysis may be promoted by adding water to the halogen-containing aromatic dish acid ester derivative. The amount of water necessary for the hydrolysis is added to the elemental aromatic phosphate acid represented by the formula (V). A stoichiometric amount of water equal to or more than a derivative (aromatically drawn phosphoric acid) The reaction temperature is not particularly limited, and is preferably a temperature above normal temperature (especially more than 4 〇. (: temperature), preferably in ribs to 丨2〇<) (: search is better. In step B) It is preferred to carry out reflux at the same time as the boiling point of the organic solvent present in the system, and the azeotropic point of the organic solvent and water. 25 201209143 As the above organic solvent, the organic solvent used in the previous reaction can be continuously used. It is also possible to use another organic solvent, and it is also possible to carry out solvent exchange of another organic solvent in the reaction system after refluxing the organic solvent in the reaction system. The type of solvent that can be used can be used as described above. The solvent mentioned in the step A is the same. In the step B, the excess water is removed after the hydrolysis, and the by-produced aromatic monophosphate is removed to the outside of the reaction system. Since the aromatic phosphate monoester is very water-soluble, the aromatic phosphodiester is completely moved to the aqueous layer without the organic solvent layer in the liquid-liquid extraction. The cyclic amine salt of the aromatic monophosphate and the cyclic amine salt of the aromatic phosphodiester also exhibit the same properties as described above. Therefore, in the final reaction of the step B, the non-uniform hydrolysis of the water-insoluble organic solvent layer and the water layer not only contributes to the single-pot continuous reaction, but also can be said to contribute to the improvement of the monoester body. An excellent synthesis method for the selectivity of the diester. Of course, after the completion of the step B, the aromatic phosphodiester can be recovered in accordance with a well-known purification method, a solid-liquid separation method, or the like, and after the resin is kneaded, the aromatics to be prepared separately can be prepared. After the phosphoric acid diester and the cyclic amine are blended, they are added to the resin component. In this case, although the aromatic phosphodiester-based water-absorbent property is not large, most of the cyclic amines and cyclic polyamine-based water-absorbing properties or hydrates are highly dehydrated after being added to the resin component. It is necessary to dry, in order to obtain the flame retardant of the present invention, there is a very laborious situation. Therefore, according to the production method of the present invention, after the end of the B step, the aromatic phosphodiester cyclic amine salt is formed by continuously performing the c step by 26 201209143 because even if it is necessary for dehydration drying, even if it is not too high Drying can also be used effectively, which is a preferred and convenient method. Step C Step c After the completion of the step B, the aromatic amine represented by the above formula (I) can be continuously synthesized by adding the cyclic amine represented by the formula (111) to the reaction system and stirring and mixing. Phosphate diester cyclic amine salt. In order to highly maintain the flame retardancy and moisture resistance as described above, the amount of the cyclic amine represented by the formula (III) is such that the ion equivalents of both of them are equal to each other in the formula (11). The stoichiometric amount of the aromatic phosphodiester is represented by the addition of an equivalent amount of a suitably selected cyclic amine salt. General formula (111) • The cyclic amine to be used may be a known one or a commercially available product. In the C step, it can also be carried out in a solvent as necessary. The solvent may, for example, be a hydrocarbon solvent such as benzene 'toluene or n-hexane; an alcohol solvent such as methanol or isopropyl alcohol; or a halogenated hydrocarbon solvent such as dichloromethane or chloroform. After the c step, the cyclic amine salt of the present invention can be specifically recovered in accordance with a well-known purification method and a solid-liquid separation method. When the cyclic amine salt of the present invention represented by the general formula (I) is synthesized according to the production method of the present invention, the production can be carried out very efficiently and efficiently, and the total step yield after recrystallization can be obtained under good conditions. A very high yield of more than 80% (relative to the phenol derivative) gives the object. In the cyclic amine salt of the present invention, for example, diphenyl hydr〇gen phosphate (DPHP), which is represented by the general formula (π), is represented by the formula (III). The cyclic amine is selected from piperazine 27 201209143, and the obtained compound is tested. When H is deleted, the chemical shift of the parenteral (methylene) 3 is from (10) ppm to 3 23 驿, in the same way. The chemical shift system of DPHP (phosphorus), WPPm to -l〇.54PPm, both of which are subjected to low magnetic field displacement. From this, it was found that the rust salt composed of the piperidinium cation and the monophenyl phosphate anion was formed by the coordination bonding with the second system. (2) Flame retardant composition containing the cyclic amine salt of the present invention The flame retardant composition of the present invention (blocking of the present invention) contains one or more kinds of the cyclic amine salts of the present invention. That is, at least one of the cyclic amine salts represented by the above (1) is contained as an active ingredient. In the cyclic amine salt of the present invention, the necessary and most important properties, namely, the wettability and water solubility, are in the present invention because there is a possibility that the aromatic phosphate monoester which may be incorporated into the cyclic amine salt causes such properties. In the flame retardant of the present invention, the amount of the aromatic monoester phosphate mixed is preferably as small as possible. That is, the content of the aromatic acid monoester in the flame retardant of the present invention is preferably 1% by weight or less, particularly preferably 1% by weight or less, and most preferably 0% by weight. Further, the aromatic phosphoric acid monoester and the aromatic phosphodiester which is the component A can be investigated for the ratio of the presence thereof by, for example, measuring LC/MS or GC/MS. Further, it can be easily confirmed by measuring the 3IP-NMR system because the chemical shift of the diester body is about 5-12 ppm to -10 ppm, and the chemical of the monoester body is about -3 ppm to -4 ppm. Further, the flame retardant of the present invention may contain, in addition to the cyclic amine salt of the present invention, an additive formulated by a well-known flame retardant. 28 201209143 In particular, the flame retardant of the present invention can suitably use a phosphate (c component). Even if only a phosphate is used as the flame retardant, it is very difficult to obtain both flame retardancy, moisture resistance and blooming resistance, but by including the cyclic amine salt and the phosphate of the present invention at the same time, In addition to highly enhancing the flame retardancy and moisture resistance, it is possible to obtain an effect of more effectively preventing blooming. As described above, in the case of the prior art flame retardant, the phosphate type is not easily blended with the synthetic resin and is not easily dispersed and stabilized. When the flame retardant resin is not well dispersed in the resin, various properties such as moldability and impact resistance of the flame-retardant resin are lowered, and most of them are likely to bleed out. On the other hand, the cyclic amine salt of the present invention has a function as a dispersion stabilizer and/or a compatibilizer in the case of a synthetic resin, and the present invention is superior to the prior art. The phosphate is not particularly limited, and examples thereof include an inorganic condensed acid ammonium salt such as U multi-filled acid, 2) an inorganic condensed phosphoric acid salt such as a coated multi-disc acid salt, and 3) At least one species of an acid, pyrophosphoric acid or a condensed acid and an organic salt composed of a tri-farming derivative.

1) The inorganic condensed ammonium phosphate salt of the above-mentioned C component, such as ammonium polyphosphate, is a commercial product, and the product name r Ex〇LIT AP422" and "EXOLIT AP·" (any one is manufactured by claRIANT) The product name "TERRAJU S-10", "TERRAJU S-20" (any one is manufactured by CHISSO Co., Ltd.), and the product name "SUMISAFE P" (manufactured by Sumitomo Chemical Co., Ltd.). 2) The inorganic condensed ammonium phosphate salt such as the coated ammonium polyphosphate, which is coated with the above-mentioned component C, is microencapsulated or cured by using a thermosetting resin in order to replenish the defects of the ammonium polyphosphate which is easily hydrolyzed by moisture absorption. It is obtained by surface treatment such as coating of melamine 29 201209143 amine cross-linking, and surface treatment of particles by using a surfactant, a ruthenium compound or the like. As an example of such a commercial product, the product name "£乂0[1丁八?462" (0^1118>1), product name "TERRAJU C-30", "TERRAJU C" -60", "TERRAJU C-70"' "TERRAJU C-80" (any one is made by CHISSO Co., Ltd.). 3) The organic salt composed of phosphoric acid, pyrophosphoric acid or an amine composed of a condensed phosphoric acid and a tri-negative derivative, and specific examples thereof include melamine, decylamine, decyl decylamine and ethyl decylamine. , benzoguanamine, benzyl decylamine, guanazie, guanidine, 2,4-diamino-6-thiofenofolin-1,3,5-three-speaking, etc. . Phosphate, pyrophosphate, and a multi-disc acid salt of a well derivative obtained by acid condensation. In the flame retardant of the present invention, a synthetic resin composition or the like can be obtained by mixing a flame retardant composition containing at least one of the cyclic amine salt of the present invention and the phosphate component of the C component in various resin components. Highly flame retardant. The flame retardant of the present invention is a phosphorus-forming type phosphorus-based nitrogen-based flame retardant, and a representative carbon-forming flame retardant, that is, red phosphorus, polybasic acid amine salt, and most of the acid-filling S And two-degree well derivatives are susceptible to significant effects on moisture. That is, the characteristic of the phosphorus-based compound is a fatal disadvantage as a flame retardant, and there are the following problems: for example, generation of a phosphine derived from red phosphorus (PHD gas, which causes a blooming phenomenon derived from polyphosphoric acid amine, which is derived from The hydrolysis of the phosphate ester is colored, and the disadvantages such as the decomposition of the amine (nitrogen)-based gas, the coloration of the resin, and the decrease in the molecular weight are caused. The disadvantages of these defects are moisture due to moisture absorption, active radicals derived from moisture, and the like. 30 201209143 That is, as a carbon-based flame retardant, it is considered that the most important practicability in practical use is the high degree of susceptibility to the lyophile (4) and the degree of hygroscopicity. Most of the carbon-based flame retardants are generally poor in resin compatibility. For example, even if added to a low-polarity polyolefin resin, the resin towel will not continue to be uniformly and stably dispersed, and a flame retardant may be used. The problem of moving to the surface of the resin and causing the mechanical properties of the resin to be very low. The flame retardant which is a part of the phosphate ester has excellent resin compatibility, but most of the system In the case of a liquid having a low melting point and a low thermal decomposition initiation temperature, the plasticity is too strong and the formability is lowered, and most of the molded article cannot provide high flame retardancy. The cyclic amine salt of the present invention is not a non-suction alone. A wet flame retardant is a case where a component having hygroscopicity is added in order to enhance flame retardancy, because the cyclic amine salt of the present invention can also serve as a kind of stable dispersion or insolubilization of c component in the resin. The task of protecting the buffer is to suppress the mobility of the surface of the molded article, the blooming phenomenon, or the surface roughness of the molded article by suppressing the hygroscopicity and maintaining the uniformity of dispersion of the flame retardant composition in the resin. Flame-retardant resin composition containing the flame retardant of the present invention (composition of the present invention) (1) Flame-retardant resin composition The present invention contains a flame-retardant resin composition containing the resistance of the present invention The resin composition of the fuel component and the resin component contains 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. The resin component is not particularly limited, for example, A synthetic resin known from the Japanese Patent Publication No. 31 201209143. More specifically, a polyolefin resin, a polystyrene resin, a polyethylene resin, a polyamide resin, a polyimide resin, and a polyester are exemplified. Resin, polyether resin, polycarbonate resin, polyacetal resin, polyether resin, polyphenylene sulfide resin, polyamidoximine resin, polyether sulfone resin, polysulfone resin , a polyester resin such as a polymethylpentene resin, a urea resin, a melamine resin, an epoxy resin, a polycarbamic acid, a resin, a resin, and the like, or a homopolymer or a copolymer of a thermosetting resin, alone or the like. A resin alloy to be combined, etc. As a preferred polyolefin-based resin of the composition of the present invention, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1 can be suitably used. a homopolymer of an α-olefin such as octene, a resin such as a monomer or a mixture of random or block copolymers between the aforementioned α-olefins, and further a copolymer with vinyl acetate or maleic anhydride A polyolefin-based resin such as a polymer obtained by polymerization. More specifically, a polypropylene-based resin such as a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene block copolymer, a propylene-ethylene-butene copolymer, or the like; A polymer, a high-density ethylene homopolymer, an ethylene-cz-olefin random copolymer, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a polyethylene resin, or the like. Further, in the present invention, in order to improve the physical properties of the flame-retardant resin composition, a polyethylene-based synthetic rubber or a polyolefin-based synthetic rubber may be blended as necessary. Examples of the polystyrene resin include polystyrene, an acrylonitrile-styrene copolymer, and an acrylonitrile-butadiene-styrene copolymer. Examples of the vinyl-based resin include a homopolymer 32 201209143 compound of a vinyl monomer such as an alkyl acrylate, an alkyl methacrylate, a vinyl acetate, or a vinyl alcohol, and a monomer of the above-mentioned Copolymer and the like. Examples of the polyamine-based resin include polydecylamine 6, polydecylamine, polyamidamine 11 sulfonamide 12-mercapto 63, polylacquer, polyamine, and polyamide 610. For example, polyethylene terephthalate, polypair as a polyester resin, butyl succinate, yttrium naphthalate - a oxime, hexaethyl acrylate, poly(1,4-cyclohexane diol) Methyl phthalate) and the like. Examples of the 4-ether-based tree ruthenium include polyphenylene ether and polyethylene sulfonate. Examples of the polystone acid-reducing tree can be exemplified by aromatic polycarbonate and aliphatic polycarbo-molecular aromatic poly-resin, which are generally exemplified by 2,2-bis(4-hydroxyphenyl). a polymer or copolymer composed of a bisphenol such as an alkane, a bis(4-hydroxyphenyl)ether system, a bis(4-hydroxyphenyl) sulfone system or a bis(4-hydroxyphenyl) sulfide system. . Further, the resin component of the composition of the present invention is obtained by kneading two or more kinds of resin components in the presence or absence of a suitable compatibilizing agent in addition to the resins of the above-mentioned respective systems. Alloy resin. Examples of the alloy resin include polypropylene/polyamide, polypropylene/polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer/polybutylene terephthalate, and acrylonitrile-butylene. Diene-styrene copolymer/polyamide's polycarbonate S/propylene syrup-butadiene styrene copolymer, polycarbonate S/poly(decyl methacrylate), polycarbonate/polyamide Polycarbonate/polyethylene terephthalate, polycarbonate/polybutylene terephthalate, and the like. Further, as the resin component, a modified product of the above-mentioned synthetic resin can also be used, and for example, an unsaturated carboxylic acid (for example, acrylic acid, sulfhydryl group 33 201209143: dilute, cis-butane diacid, and butyl dicarboxylic acid can also be used. A modified product obtained by grafting a synthetic resin, such as cis-butyl diacid sulphate, yin yin liver* or broken oxygen. Among the above-mentioned resin components, from the viewpoint of obtaining a molded article having a higher generality and a balance, it is particularly preferable to use a combination of a dipropylene compound and a flame retardant of the present invention. In particular, it contains a poly-collinated polymer, an ethylene-based material, and a 6-thick, alkene block, and a composition of the present invention. The composition of the composition of the present invention is resistant to skin formation, resistance to damage, and resistance. It is better to be able to perform the special performance that is not available. The compounding ratio of the cyclic amine salt of the present invention is not particularly limited, and may be added to the degree of the ageing property and the flame retardancy. In particular, in order to maintain kneading stability and formability, in order to further impart moisture resistance and high flame retardancy to the molded article, 1 the cyclic amine salt of the present invention is blended with 1 GG by weight of the resin component. ~ _ parts by weight, more preferably _ parts by weight, weight parts can be. When the blending ratio of the flame retardant is less than i by weight, the flame retardancy is not filled, and on the other hand, when it exceeds 100 parts by weight, the properties originally possessed by the resin may not be obtained. Further, by adding the above-mentioned C-forming blade in addition to the cyclic amine salt of the present invention, the carbonization-promoting effect of foaming (a disc salt such as an amine, a tri-n-well or a melamine) is used for the composition of the present invention. The carbon forming property is also multiplied, and a higher degree of flame retardancy can be obtained. In the resin composition containing the flame retardant composition and the resin component of the present invention, the ratio of the cyclic amine salt of the present invention is set to 1 to 50 parts by weight based on 100 parts by weight of the resin component. Further, the component c is preferably 1 to 50 parts by weight, and more preferably 10 to 30 parts by weight of the cyclic amine salt of the present invention and more preferably 1 to 30 parts by weight of the component C. In the composition of the present invention, in addition to the above-described components, a well-known or commercially available additive may be appropriately blended as necessary within a range that does not impair the effects of the present invention. Examples of the antioxidants such as a phenol compound, a phosphine compound, and a thioether compound; and ultraviolet absorption of a diphenyl ketone compound, a benzotriazole compound, a salicylate compound, a hindered amine compound, and the like Agent or light stabilizer; cationic compound, anionic compound, nonionic compound, amphoteric compound, metal oxide, lanthanide conductive molecular compound, antistatic agent such as carbon, and conductive agent; fatty acid, fatty guanamine, fat a slip agent such as an acid ester or a fatty acid metal salt; a benzylidene sorbitol-based compound nucleating agent; a filler of talc, calcium carbonate, barium sulfate, mica, glass fiber, glass beads, low-melting glass, etc.; Chemical agent, coloring agent, anti-blooming agent, surface modifier, anti-adhesive agent, anti-fogging agent, adhesive, gas adsorbent, freshness retaining agent, enzyme, deodorant, perfume, etc. As the drip control agent of the composition of the present invention, a polytetrafluoroethylene-containing mixed particle powder having fibril forming properties may be added. By adding a polytetrafluoroethylene-containing mixed particle powder having fibril forming properties, the flammability test of the flame-retardant resin composition, especially the UL specification_direct combustion test (UL94V) can improve combustion. The test piece prevents dripping performance. Heart, as the polytetraethylene-containing mixed plate powder having fibril forming properties, for example, polytetrafluoroethylene or tetragas (10) cerium polymer is preferable, and polytetrafluoroethylene (PTFE) is preferred. 35 201209143 In this case, the average particle diameter of the powder is not particularly limited, and it is usually about 0.1 to 1000 Am. In addition, it is preferable to set the amount of the resin component in an amount of usually 0.01 to 10 parts by weight, based on the amount of the resin component which is usually required to be in the range of 0.01 to 10 parts by weight. (2) Method for Producing Flame Retardant Resin Composition The composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can be produced by melt-kneading each of the above components. The kneading sequence at this time is not particularly limited, and each of them may be mixed at the same time, or a plurality of types may be mixed in advance and the remaining portions may be mixed later. The mixing method is not limited to, for example, a high-speed agitator such as a drum type V-type blender, a Schneider mixer, a spiral blade type mixer, a uniaxial, biaxial continuous kneader, a roll mixer, or the like can be used. The method of using the device alone or in combination. Further, the present invention can also use a composition having a high concentration of synthetic resin as a master batch, and then further mixing and diluting with a resin to obtain a predetermined resin composition. (3) Use of a flame retardant resin composition because The composition of the present invention can effectively suppress bleeding while achieving excellent flame retardancy, and can be suitably used as a molded article. That is, the flame-retardant resin composition of the present invention can be suitably used as a resin composition for producing a shaped article. Thereby, a molded article excellent in flame retardancy can be provided. 3. Molded article The present invention also includes a flame-retardant resin molded article obtained by molding the flame-retardant resin composition of the present invention. 36 201209143 The molding method is not particularly limited, and for example, a well-known molding method such as injection molding or extrusion molding can be used. For example, a method in which a sheet is temporarily formed by a method using an extrusion molding machine, a secondary processing such as vacuum forming or press forming, a method of forming by an injection molding machine, etc., but generality is used. In terms of height, the present invention is particularly excellent in injection molding. In the injection molding, not only the usual hot and cold runner method, but also a hot runner without sprue can be used to produce a molded article. Further, for example, gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, or the like can be employed. The molded article comprising the flame-retardant resin composition of the present invention can be applied to applications in which the flame retardancy of home electric appliances, OA products, and automobiles is considered to be necessary. Specifically, it can be suitably used for various types of automobiles, ships, aircraft parts, and washstand parts, such as insulating covering materials such as electric wires and cables, various electric parts, gauge boxes, lamp covers, bellows, wire covering materials, and battery parts. Various table materials such as potty parts, bathroom parts, floor heating parts, lighting fixtures, air conditioners, etc., roofing materials, ceiling materials, wall materials, flooring materials, etc., TV, radio, video/recording machine, washing machine, refrigerator Uses such as household electric products such as vacuum cleaners, electric cookers, and lighting machines. EXAMPLES Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto. Further, various physical properties of the respective compounds obtained in the following synthesis examples and the like are measured as follows. 37 201209143 (1) Purity A gas chromatograph (GC-2010: Shimadzu Corporation) and a photodiode array (PDA; photodiode array) with a high-speed liquid gas layer with a three-dimensional UV detector The analyzer (ALLIANCE HPLC SYSTEM: manufactured by Waters Co., Ltd.) was used to confirm the purity. (2) Melting point

The melting point was measured using a fully automatic melting point measuring apparatus (FP-62: manufactured by METTLER TOLEDO Co., Ltd.). (3) Elemental analysis Elemental analysis was performed for each element, and carbon, hydrogen, and nitrogen were analyzed using (EA1110: CE INTRUMENTS), and the high-frequency combination was used after wet decomposition using a microwave sample decomposition apparatus (ETHOS1: MILESTONE GENERAL). A plasma luminescence analyzer (ICP-OES: manufactured by VARIAN Co., Ltd.) analyzed phosphorus. (4) Structure analysis: Gas chromatograph (GCMS-2010Plus: Shimadzu Corporation) manufactured by the infrared absorption analyzer (FT-IR, FT-720, Ltd.) Hydrogen nuclear magnetic resonance (iH-NMR) spectrum and phosphorus nuclear magnetic resonance (31P-NMR) spectrum of a 300 MHz nuclear magnetic resonance absorption analysis apparatus (JNM-AU00: manufactured by JEOL Ltd.) were used to identify the structures of the respective compounds. <Synthesis Example 1> 1. Synthesis of diphenyl hydrogenphosphate piperazine 1.1 Synthesis of diphenyl chlorophosphate (DPCP) 38 (17) (17)201209143 20]

In a four-necked flask equipped with a cooler, a dropping funnel with a side tube and a thermometer, and a mixing device, 94.1 g (1.0 mol) of benzene, 76.67 g (0.5 mol) of phosphorus oxychloride and 700 g of stupid were charged. And, 106.25 g (1. 5 mol) of triethylamine was put in the side tube dropping funnel. After the gasification calcium tube is installed at the upper end of the cooler so that the moisture in the air does not mix into the reaction system, the flask is kept at 3 (TC) while stirring in a nitrogen atmosphere. After the stirring is started, the reaction is started. The triethylamine was dropped from the dropping funnel at a temperature of not more than 40 ° C for 2 hours. After the completion of the dropwise addition, the reaction was aged for 1 hour, and the sample was sampled and the reaction product was measured by GC/MS. The purity of the reaction intermediate of the yellow transparent liquid was 98% or more. From the molecular ion peak of the GC/MS spectrum (M+: m/z 268), it was confirmed that the diphenyl chlorophosphate represented by the above formula (17) was obtained (DPCP: Mw 268.63) as a reaction product. 1.2 Synthesis of diphenyl hydrogen phosphate (DPHP; diphenyl hydrogenphosphate) [Chem. 21]

From the above, after confirming that the phenol of the raw material contained in the reaction product completely disappeared by GC/MS, the flask was cooled to 20 ° C using a constant temperature water bath, and 140 g of water was placed in the flask and stirred for 30 minutes. After the completion of the stirring, the reaction solution was allowed to stand for 30 minutes to separate the organic layer from the aqueous layer, and the aqueous layer was taken out. Using an incandescent cover while adding 39 201209143 The flask was heated while slowly heating the flask, and the toluene in the reaction liquid was distilled off until the temperature of the reaction liquid in the flask reached 120 °C. When the distillation amount of toluene was 560 g, the heating was temporarily stopped, and after cooling the reactant to 80 ° C, '14 g of water was charged and reheated, and toluene was removed from the reaction system by azeotropy of toluene and water. Hydrolysis of diphenyl hydrogenate (DPHP) was carried out by refluxing for 2 hours. After cooling to room temperature, 300 g of ethyl acetate was placed in the flask and stirred, and then re-layered to take out the aqueous layer. After the organic layer was washed with water, the reaction product in the organic layer was sampled to confirm the purity of the reaction intermediate, and the degree was about 99% or more (HPLC). When the reaction product was completely dried under reduced pressure, it was a white solid having a melting point of 69 °C. From the results of 1H-NMR measurement and 3IP-NMR measurement of the compound, it was confirmed by 1H-NMR that the obtained reaction product was diphenyl hydrogen phosphate (DPHP) represented by the above formula (18). 1H-NMR (300MHz, DMSO-d6): 5/ppm 7.1 l-7.23 (4H, m) ' 7-29-7.40 (6H, m) 31P-NMR (109MHz, DMSO-d6): 5/ppm -11.31 Synthesis of h3 diphenyl hydrogen phosphate piperazine (DPHPP) [Chem. 22]

Continuing with the above 1.2, the organic layer containing the reaction product, that is, diphenyl phosphate 40 201209143 (DPHP), was dissolved in 1 μg of methanol and dissolved in a dropping funnel with a side tube. 2丨5g (〇.25m〇i) of 2哌g sterol in anhydrous piperage solution. When the anhydrous piperage solution was dripped for 2 hours while stirring the reaction liquid, a white solid precipitated. The white solid was recrystallized from methanol/water (2/1, wt) to give 117.1 g (yield: 20%) of white crystal powder. The white crystalline powder has a melting point of 2〇2.2. Further, from the results of b-NMR measurement and 31P-Nmr measurement of the compound, and the results of elemental analysis described below, it was confirmed that the obtained reaction product was hydrogen phosphate represented by the above formula (19). Phenyl ester pipedrine (DPHPP). 'H-NMR (300 MHz, DMSO-d6): 6/ppm 3.23 (8H, s) ' 6.96-7.01 (4H, m), 7.11-7.14 (8H, m), 7.20 -7.27(8H,m) 31P-NMR (109MHz, DMSO-d6): 5/ppm -10.54 Elemental analysis 〇281^32 〇8?2(^^586.51), calculated: C, 57.34; H, 5.50 ;N, 4.78; P, 10.56 Found: C, 57.13; H, 5.52; N, 4.77; P, 10.54 <Synthesis Example 2) 2. Dihydrogen phosphate dip-tolyl hydrochloride salt (DTHPP; di-p- Synthesis of tolyl hydrogenphosphate piperazine) 2.1 Synthesis of acid-to-liquid di-p-tolyl chlorophosphate (Chem. 23)

108.14 g (1.0 mol) of p-phenol was used in place of the above-mentioned phenol, and by 41 201209143, the reaction of the obtained yellowish transparent liquid was obtained by sampling and measuring the reaction product by GC/MS in the same manner as in the above 1.1. The purity of the substance was 98% or more. From the molecular ion peak (M+: m/z 296) of the GC/MS spectrum, it was confirmed that the dichloro-p-tolyl phosphate (DPCP: Mw 296.69) represented by the above formula (20) was obtained as a reaction. Product. 2.2 Synthesis of di-p-tolyl hydrogenphosphate (DTHP) [Chem. 24]

〇 II

-P—〇 I

0H The procedure shown in the above 2.1 was continued, and the same operation as in the above 1.2 was carried out, and when the purity of the obtained reactant was confirmed by sampling, the purity was 99% or more (HPLC). When the reaction product was completely dried under reduced pressure, it was a white solid having a melting point of 79t. From the results of 1H-NMR measurement and 31 P-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydroto-hydrogen phosphate (DPHP) represented by the above formula pi). 'H-NMR (300MHz, DMSO-d6): 8/ppm 2.25 (6H, s) ' 7.03-7.08 (4H, m), 7.12-7.17 (4H, m). 3'P-NMR (109MHz, DMSO- D6): 8/ppm - 10.91 2.3 Synthesis of dihydrogenated dip-tolyl hydrogen phosphate piperazine (DTHPP; di-p-tolyl hydrogenphosphate piperazine) 42 201209143 [Chem. 25]

The procedure shown in the above 2.2 was continued, and 112.5 g (0.18 mol, yield 70%) of white crystal powder was obtained by the same operation as the above. The white crystalline powder had a melting point of 206.2 °C. Further, from the results of 1H-NMR measurement and 31P-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained reaction product was di-p-tolyl phosphate represented by the above formula (22). Drilling salt (DTHPP). 1H-NMR (300MHz, DMSO-d6): 5/ppm 2.21(12H, s) ' 3.21 (8H, s) ' 6.98-7.05 (16H, m) 3, P-NMR (109MHz, DMSO-d6): 5 /ppm -9.97 Elemental analysis C32H4〇N208P2 (Mw 642.62), calculated: C, 59.81; H, 6.27; N, 4.36; P, 9.64 Measured · · C, 59_43; H, 6.08; N, 4.32; 9.63 <Synthesis Example 3> 3. Synthesis of di-2,6-dioxyl hydrogen phosphate piperazine (DXHPP; di-2,6-xylenyl hydrogenphosphate piperazine) 3.1 Chlorochloride di-2,6-xylene Synthesis of ester (DXCP; di-2,6-xylenyl chlorophosphate) 43 201209143 [Chem. 26]

122.16 g (1.0 mol) of 2,6-xylenol was used in place of the phenol of 1.1, and the resulting yellowish transparent liquid was obtained by sampling and measuring the reaction product by GC/MS by the same operation as in the above 1.1. The purity of the reaction product was 99% or more. From the molecular ion peak of the GC/MS spectrum (M+: m/z 324), it was confirmed that the chlorodi-2,6-xyl phosphate represented by the above formula (23) was obtained. DXCP: Mw 324.74) is used as a reaction product. 3.2 Synthesis of di-2,6-xylylene phosphate (DTHP; di-2,6-xylenyl hydrogenphosphate) [Chem. 27]

The procedure shown in the above 3.1 is continued, and the same operation as in the above 1.2 is carried out, and when the purity of the obtained reactant is confirmed by sampling, the purity is 98% or more (HPLC). When the reaction product was completely dried under reduced pressure, it was a white solid m.p. From the results of the iH-NMR measurement and the 31 P-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydrogen-2,6-xylylene phosphate (DXHP) represented by the above formula (24). A-NMR pOOMHz'DMSO-c^j/ppm 2.27 (12H, s), 6.95-7.06 (6H, m) 44 201209143 3*P-NMR (109MHz, DMSO-d6) j/ppm -9.97 3.3 Hydrogen phosphate di- Synthesis of 2,6-xylylene hydrochloride (DXHPP; di-2,6-xylenyl hydrogenphosphate piperazine) [Chem. 28]

The procedure shown in the above 3.2 was continued, and 108.3 g (0.16 mol of 'yield 62%) of white crystal powder was obtained by the same operation as the above. The white crystalline powder had a melting point of 224.2 °C. Further, from the results of 1H-NMR measurement and 3IP-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained reaction product was hydrogen-2,6 represented by the above formula (25). - Diphenyl benzoic acid salt (0乂11??). 1H-NMR (300MHz, DMSO-d6): 8/ppm 2.28(24H,s) ' 2.97 (8H,s) ' 6.81-6.85(4H,m) ' 6.93-6.95(12H,m) 3'P-NMR (109MHz, DMSO-d6): 8/ppm -8.49 Elemental analysis C36H48N208P2 (Mw 698.72), calcd: C, 61.88; H, 6.92; N, 4.01; P, 8.87 Found: C, 61.63; H, 6.85; N, 3.98; P, 8.81 <Synthesis Example 4> 45 201209143 4·Synthesis of dihydrogen phosphate _4·t-butyl hydrogenated piperazine (DSHPP; di-4-t-butyl hydrogenphosphate piperazine) 4.1 Phosphate gas II Synthesis of 4-tert-butyl ester (DBCP; di-4-t-butyl chlorophosphate) [Chem. 29]

The reaction of the obtained yellowish solid was carried out by using 150.22 g (1.0 mol) of 4-t-butylphenol in place of the phenol of the above 1.1, and sampling and measuring the reaction product by GC/MS by the same operation as the above 1.1. The purity of the substance was 97% or more, and the melting point was 101.0 °C. Further, from the molecular ion peak (M+: w/z380) of the GC/MS spectrum, it was confirmed that the phosphoric acid gas di-4-tert-butyl ester (DXCP: Mw 380.85) represented by the above formula (25) was obtained as a reaction product. . 4.2 Synthesis of di-4-t-butyl hydrogen phosphate (DBHP; di-4-t-butyl hydrogenphosphate) [Chem. 30]

The procedure shown in the above 4.1 is continued, and the same operation as in the above 1.2 is carried out, and when the purity of the obtained reactant is checked by sampling, the purity is 98% or more (HPLC). When the reaction product was completely dried under reduced pressure, it was a pale reddish brown solid having a melting point of 137.4 °C. From the results of 1H-NMR measurement and 3IP-NMR measurement of the compound, it was confirmed that the obtained reaction product was di-4-tert-butyl phosphate (DBHP) represented by the above formula (27). 46 201209143 'H-NMR (300MHz, DMSO-d6): 5/ppm 1.26(18H,s) '7.08-7.11(4H,m), 7.35-7.38(4H,m) 31P-NMR (109MHz, DMSO-d6 ): 5/ppm -10.88 4.3 Synthesis of di-4-t-butyl hydrogen phosphate piperazine (DBHPP; di-4-t-butyl hydrogenphosphate piperazine) [Chem. 31]

The procedure shown in the above 4.2 was continued, and 162.2 g (0.20 mol, yield: 80%) of pale yellowish white crystal powder was obtained by the same operation as the above. The white crystalline powder had a melting point of 252.1 °C. In addition, from the results of the b-NMR measurement and the 31P-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained reaction product was the hydrogen phosphate di-4-methyl represented by the above formula (28). Tributyl ester pipedrine salt (DXHPP). 1H-NMR (300MHz, DMSO-d6): 6/ppm 1.23 (36H, s) ' 3.18 (8H, s), 7.02-7.05 (8H, m), 7.20-7.24 (8H, m) 31P-NMR (109MHz , DMSO-d6): 5/ppm -10.04 Elemental analysis C44H64N208P2 (Mw 810.94), calcd: C, 65_17; H, 7.95; N, 3.45; P, 7.64 Found: C, 65.30; H, 7.89; 3.47; Ρ,7·61 47 201209143 <Comparative Example ι> 5. Synthesis of phenyl dihydrogenphosphate piperazine (PDHPP; phenyl dihydrogenphosphate piperazine) 5.1 phenyl dichlorophosphate Synthesis [32]

In a 4-necked flask equipped with a stirrer and a thermometer and a thermometer, 94.11 g (1.00 mol) of phenol, 459.99 g (3.00 mol) of hydroxyphosphorus phosphide and 2.73 g of (z) 2 mol of zinc chloride were charged. After the vaporized calcium tube was installed at the upper end of the cooler so that moisture in the air did not enter the reaction system, stirring was started under a nitrogen atmosphere and the temperature was gradually raised using an incandescent heater. Since hydrogen chloride gas was generated in the reaction, it was heated to 80 °C in 5 hours without causing a sudden boiling. Subsequently, it was confirmed by GC and HPLC that the peak of phenol disappeared in the reaction product. In order to distill off excess hydroxylated phosphorus in the reaction product, distillation under reduced pressure was carried out by distilling off the temperature at 34 to 100 ° C and a vacuum of 50 Torr to obtain 291 g of hydroxy-vaporated phosphorus (recovery rate was 95%). ). The reaction product was further distilled at a temperature of 118 to 120 ° C and a vacuum of 6 Torr to obtain a colorless transparent liquid of 159.92 (0.76 mol: yield: 75.8%). The purity of the compound was 99% or more ( GC), and the boiling point is 243 ° C / 760 Torr. From the molecular ion peak (M+: m/z 210) of the GC/MS spectrum of the compound, it was confirmed that the dialkyl phosphate (PDCP: Mw 210.98) represented by the above formula (29) was obtained. 5.2 Synthesis of dihydrophenyl ester (PDHP; Phenyl dihydr〇gen PhosPhate) 48 201209143 [Chem. 33]

OH A four-necked flask equipped with a stirrer and a cooler and a thermometer was charged with 159.92 g (〇_76 mol) of diphenyl benzene vinegar and 341.1 g (18.95 mol) of water. After the stirring was started, the mixture was heated under reflux for 5 hours, and it was confirmed by GC that the peak of dichlorophenyl phosphate disappeared. The reaction liquid was concentrated and dried using an evaporator to obtain a red viscous liquid. The solid is precipitated by triturating the viscous liquid using dichlorosilane. By washing and drying the solid using dioxane, 110.85 g (0.64 mol: yield: 84.0%) of pale white solid was obtained. The obtained compound had a purity of 99% or more (HPLC) and a melting point of 100.0 °C. Further, from the results of the W-NMR measurement and the 31 P-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydrophenylphenyl phosphate (PDHP) represented by the above formula (30). 1 H-NMR (300 MHz 5D2O): δ/ppm 6.86-6.89 (3H, m), 7.03-7.08 (2H, m) 31P-NMR (109MHz, D2O): 5/ppm -4·10 5.3 Dihydrogenation Synthesis of phenyl dihydrogenphosphate piperazine (Phase 34)

In a four-necked flask equipped with a cooler, a dropping funnel with a side tube, and a thermometer equipped with a stirring device, 110.85 g (0.64 mol) of dihydrogenphenyl phosphate and 998 g of 49 201209143 methanol were charged. The well was placed in a side pipe dropping funnel to be predissolved in 494 g of methanol to form 86.148 (0.640101) 11 bottom 11 well. After the start of the stirring, the cultivating solution was dropped from the dropping funnel at room temperature for 1 hour, and after the completion of the dropwise addition, the white cotton-like product was precipitated after further mixing. After the product was washed with decyl alcohol, 154.71 g (0.60 mol: yield: 95.0%) of white solid was obtained by drying. The purity of the obtained compound was 99% or more (HPLC), but did not show a clear melting point. Further, from the results of 1H-NMR measurement and 31P-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained compound is a dihydrophenyl phenyl phosphate salt represented by the above formula (31). (PDHPP). 'Η-ΝΜ^ΒΟΟΜΗζ^Ο)^^!!! 3.19-3.20(8H,m) ^ 7.01-7.10(3H,m), 7.23-7.29(2H,m) 3lP-NMR(l〇9MHz, D20) : 8/ppm -1.51 Element 260.23), Calculated: C, 46.15; H, 6.58; N, 10.77; Ρ, 11.90 Found: C, 45.91; H, 6_33; N, 10.61; P, 11.85 < Comparative Example 2> 6. Synthesis of p-tolyl dihydrogenphosphate piperazine (TDHPP) 6.1 Synthesis of p-tolyl dichlorophosphate (TDCP) [Chem. 35]

(3 2) 50 201209143 108.14 g (1.0 mol) of p-phenol was used in place of the phenol of the above 5.1, and a yellow transparent liquid of 174.16@ (0-77 mol: yield 77.4%) was obtained by the same operation as the above. When the GC/MS of the compound was measured, the purity of the obtained compound was 98% or more, and it was confirmed from the molecular ion peak (M+: m/z224) of the GC/MS spectrum that the phosphoric acid represented by the above formula (32) was obtained. Gas phenyl ester (TDCP: Mw 223.96) was used as a reaction product. 6_2 Synthesis of diterpene toluene g (TDHP; p-t〇lyl dihydrogenphosphate) [Chem. 36]

The procedure shown in the above 6.1 was continued, and the same operation as in the above 5.2 was carried out to obtain 116.48 g (0.62 mol: yield: 80.0%) of a white solid (melting point 98-7 ° C). When the purity of the obtained reactant was confirmed, the purity was 98% or more (HPLC). From the results of the b-NMR measurement and the 31P-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydro-p-tolyl phosphate (TDHP) represented by the above formula (33). 1H-NMR (300MHz, D2O): 6/ppm 2.05 (3H, s) ' 6.84-6.87 (2H, m) ' 6.95-6.98 (2H, m). 3IP-NMR (109MHz, D2O): 6/ppm - 3.89 6.3 Synthesis of p-tolyl dihydrogenphosphate piperazine (TDHPP; p-tolyl dihydrogenphosphate piperazine)

(3 4) 51 201209143 The procedure shown in the above 6.2 was continued, and the same operation as in the above 5.3 was carried out to obtain 152.83 g (0-56 mol, yield 90.0%) of a white solid. The purity of the obtained compound was 99% or more (HPLC), but no clear illusion was shown. In addition, from the results of 1H-NMR measurement and 3IP-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained reaction product was dihydro-p-tolyl phosphate represented by the above formula (34). Morphine salt (TDHPP). 'H-NMR (300MHz, D20): 6/ppm 2.15(3H,s)' 3.19(8H,s) > 6.94-6.96(2H,m), 7.03-7.06(2H,m) 3,P-NMR (109MHz, D2O): 6/ppm -0.87 Elemental analysis ChHipNsC^PCFw 274.25), calculated: C, 48.17; H, 6.98; N, 10.21; P, 11.29 Found: C, 48.00; H, 7.06; 10.21; P, 11.21 <Comparative Example 3> 7. Synthesis of 2,6-xylenyl dihydrogenphosphate piperazine of dihydrogen phosphate (XDHPP; 2,6-xylenyl dihydrogenphosphate piperazine) Synthesis of xdcp; 2,6-xylenyl dichlorophosphate [Chem. 38]

Using 122.16 g (1.0 mol) of 2,6-dimethylphenol in place of the above-mentioned 5" benzene, and by the same operation as the description of 5.1, a brown liquid of up to 4 g (1.0 mol: yield 100) was obtained. %). When the gc/ms of the compound was measured, the purity of the compound obtained from 52 201209143 was 95% or more, and it was confirmed from the molecular ion peak (M+: m/z 238) of the GC/MS spectrum that the compound represented by the above formula (35) was obtained. 2,6-diphenyl phenyl dichloride (XDCP: Mw 237.97) was used as a reaction product. 7.2 Synthesis of dihydrogen phosphate 2,6-xyl ester (XDHP; 2,6-xylenyl dihydrogenphosphate) [Chem. 39]

The procedure shown in the above 7.1 was continued, and the same operation as in the above 5.2 was carried out to obtain 87.93 g (0.44 mol: yield: 43.5%) of a white solid (melting point 139.0 ° C). When the purity of the obtained reactant was confirmed, the purity was 98% or more (HPLC). From the results of W-NMR measurement and 3 i-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydrogen 2,6-diphenyl phenyl phosphate (XDHP) represented by the above formula (36). b-NMRpOOMHz^OW/ppm 2.16(6H,s), 6.84-6.89 (lH,m), 6.94-6.96(2H,m). 31P-NMR(109MHz,D2O)A/ppm _3.83 7.3Dihydrogen phosphate Synthesis of 2,6-xylenyl dihydrogenphosphate piperazine (XDHPP; 2,6-xylenyl dihydrogenphosphate piperazine)

53 201209143 Continuing the procedure indicated in the above 7.2, a white solid of 111.23 ru (0.39111 〇 1, yield 88.70 / 〇) was obtained by performing the same operation as in the above 5.3. The obtained compound had a purity of 99% or more (HPLC), but did not show a clear grafting point. Further, it was confirmed from the results of b-NMR measurement and 31p_NMR measurement of the compound and the following elemental analysis that the obtained reaction product was dihydrogen phosphate 2,6-xylene represented by the above formula (37). Ester piperidin (XDHPP). 'Η-ΝΜΚ(300ΜΗζ,〇2〇): δ/ρριη 2.17(6H,s) &gt; 3.09(8H,s) ' 6.80-6.84(1H,m),6.91-6.94(2H,m) 31P-NMR (1〇9MHz, D20): 5/ -1.75 Elemental analysis Cl2H2lN204P (Fw 288.28), calculated: C, 50.00; H, 7.34; N, 9.72; P, 10.74 Found: C, 49.91; H, 7.29; , 9.69; P, 10.61 <Comparative Example 4&gt; 8. Synthesis of 4-t-butyl dihydrogenphosphate piperazine (BDHPP) 8.1 Dimethyl phosphate 4-tert-butyl ester (BDCP) Synthesis of 4-t-butyl dichlorophosphate) [Chem. 41]

150.22 g (1.0 mol) of 4-t-butylphenol was used instead of the phenol of the above 5.1, and 267.09 g of a brown liquid (1.0 mol: yield 100%) was obtained by the same operation as the above. When the GC/MS of the compound was measured, the purity of the compound obtained in 54 201209143 was 95% or more. From the molecular ion peak (M+: m/z 266) of the GC/MS spectrum, it was confirmed that the compound represented by the above formula (38) was obtained. Dihydrogen phosphate 4-tert-butyl phosphate (BDCP: Mw 266.00) was used as a reaction product. 8.2 Synthesis of dihydrogen phosphate 4-tert-butyl diester (BDHP; 4-t-butyl dihydrogenphosphate) [Chem. 42]

The procedure shown in the above 8_1 was continued, and the same operation as in the above 5.2 was carried out to obtain a yellow solid (yield: 96.2 ° C) of 115.56 lv (0.5111 〇1: yield: 50.2%). When the purity of the obtained reactant was confirmed, the purity was 97% or more (HPLC). From the results of the iH-NMR measurement and the 31p-NMR measurement of the compound, it was confirmed that the obtained reaction product was dihydrogen 4-tetrabutyl phosphate (XDHP) represented by the above formula (39). 'H-NMR (300MHz, D2O): δ/ppm 1.14 (9H, s) &gt; 6.97-7.02 (2H, m) ' 7.29-7.34 (2H, m). 31P-NMR (109MHz, D2O): 6/ Synthesis of ppm -3.73 8.3 dihydrogen 4-tert-butyl peptide salt (BDHPP; 4_t_butyl dihydrogenphosphate piperazine)

[Continuing the procedure shown in the above 8.2] By performing the same operation as above, a white solid of 135 g (yield: 43. The obtained compound had a purity of 99% or more (HPLC)' but did not show a melting point of 55 201209143. Further, from the results of 1H-NMR measurement and 31P-NMR measurement of the compound, and the results of the following elemental analysis, it was confirmed that the obtained reaction product was dihydrogen phosphate 4-third represented by the above formula (40). Butyl ester pipedrine (BDHPP). , H-NMR (300MHz, D20): 6/ppm 1.19(9H, s)' 3.15(8H, s) ' 7.03-7.06(2H,m) ' 7.33-7.36(2H,m) 31P-NMR (109MHz, </ RTI> <RTIgt; 9.71 2. Preparation of Flame Retardant Synthetic Resin Composition The flame retardant synthetic resin composition was prepared by using the cyclic amine salt obtained in each of the above Synthesis Examples. The components constituting the flame-retardant synthetic resin composition are composed of a synthetic resin and a flame retardant, and the respective components are shown below. The following components were dry blended according to the blending ratio (parts by weight) of Tables 1 and 2, and then melt-mixed using a biaxial extruder, and kneaded and kneaded, and the strands were cut. A particulate flame retardant composition. As a twin-screw extruder, a two-axis extruder "KTX30" manufactured by Kobe Steel Co., Ltd. (with a screw diameter of 30 mm, L/D = 37, and a vent hole) was used. (1) Synthetic resin Sumitomo NOBLENAY564 (Sumitomo Chemical Co., Ltd., PP) (2) Flame retardant DPHPP: Diphenyl phosphate diptomidine DTHPP: Insult | Acid argon di-p-phenyl ester &quot;丼 salt 56 201209143 0乂1^?: acid hydrogen di-2,5-diphenyl ester &quot; bottom. Barium salt BDHPP: di-4-tert-butylphenyl phosphate piperazine salt PDHPP: dihydrophenyl phenyl phosphate piperazine salt THPPP: dihydro-p-tolyl phosphate piperazine salt 乂 01 ^: dihydrogen phosphate - 2,5-Dimethyl ester piperidine salt BDHPP ··Dihydro-4-tert-butylphenyl acid sulphate APP: Exolit AP422 (ammonium polyphosphate manufactured by CLARIANT) cAPP : Exolit AP462 (melamine manufactured by CLARIANT) Coating of ammonium polyphosphate) 3. Evaluation of a molded article of a flame-retardant resin composition A molded article was produced by an injection molding method using the flame-retardant resin composition obtained above. In the injection molding system, a molding machine "FE80S type" (closed mold pressure: 80 ton) was produced by using Nissei Resin Industrial Co., Ltd. After the various test pieces obtained by the injection molding were subjected to the state adjustment treatment for 23 hours under the conditions of 23 ° C and 50% RH, the initial combustion property evaluation, the moisture resistance evaluation, and the bleeding evaluation were performed. Further, the re-combustibility evaluation was performed after the moisture resistance test. The results of these are shown in Tables 1 and 2. Moreover, these evaluation methods are specifically performed by the following methods. (1) Combustibility The evaluation of flammability was carried out according to the UL94 vertical burning test method, and a 1.6 mm (l/16 inch) thick and 0.8 mm (l/32 inch) thick UL test piece was produced and subjected to a burning test. The results of the UL94 vertical burning test were evaluated in four stages of "V-0", "V-1", "V-2", and "bad", and (2) exudation test 57 201209143 made of 2mm/3mm thick black After the flat test piece (addition of iphr carbon black), it was heated at 150 ° C for 7 days, and then the test piece was 23 . (:, 500/〇Rh conditions, after 48 hours of aging treatment, visually observed the presence or absence of oozing of the flame retardant on the surface of the test piece. Moreover, the result of the moisture resistance test was "〇 (no oozing was observed at all)", "△ (a few exudations were observed)", "x (a significant exudation was observed, or a frost was observed)", "xx (a significant exudation was observed, or a frost was observed, and a test piece crack was observed) (4) Evaluation of the moisture resistance test after making a 1.6 mm (l/16 inch) thick and 〇.8 mm (l/32 inch) thick UL test piece at 60 ° C, 90% Rh After the high humidity state was treated for 30 days, the test piece was subjected to aging treatment at 23 ° C and 50% Rh for 48 hours, and then the surface of the test piece was visually observed for the presence or absence of bleeding of the flame retardant. The results of the moisture resistance test were The evaluation was carried out in three stages of "〇 (no oozing is observed at all)", "△ (some oozing is observed)", "&gt;&lt; (significant oozing was observed, or blooming was observed)" 58 201209143 UL94 It’s not good, it’s not good, it’s not good, it’s not good, it’s not good Not good, not good, bad, bad, bad, bad, not good, 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm 0.9mm UL94V Judgment is not good, not good, not good: Not good, not good, not good, not good, not good, not good, not good, bad, bad, bad, bad, bad, bad, not good, not good, thickness, 0.9mm, 16mm, 0.9mm, 16mm, 0.9mm, 16mm, 0.9mm, 16mm, 0.9mm, 16mm, 0.9mm Mm 16mm 0.9mm 16mm 0.9mm 16mm 0.9mm 16mm 0.9mm 16mm 0.9mm 16mm Exudation test has no change in appearance, oozing, blooming, oozing, sd ' Φ-κ 忝 ad, no change in appearance, no change in appearance No change in appearance, no change in appearance. V0 slope•33 Fully involved, blooming 〇 XX &lt;&lt; 〇〇〇〇X Moisture resistance XXX &lt;] 〇〇〇〇XX Deploying cAPP 1 1 1 1 1 t 1 1 1 1 APP 1 1 1 1 1 1 1 1 1 1 BDHPP 1 1 1 1 1 1 1 1 1 1 DXHPP 1 1 1 1 1 1 1 1 1 1 DTHPP 1 1 1 1 1 1 1 1 1 DPHPP 1 1 1 1 1 1 1 1 BDHPP 1 1 1 1 1 1 1 1 1 1 XD HPP 1 1 1 沄1 1 1 1 1 1 1 TDHPP 1 1 1 1 1 1 1 1 1 1 PDHPP 1 1 1 1 1 1 1 1 1 1 Resin ο 〇〇〇〇〇〇〇〇〇〇 Blank Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Comparative Example 5 Comparative Example 6 59 201209143 UL94 Determination 5 5 5 5 S: 5 5 5 5 5 5 5 5 5 5 Thickness 0.9 mm 1.6mm 0.9mm 1.6mm 1 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm | 0.9mm 1.6mm | 0.9mm 1.6mm &gt; Judgment 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 UL9^ Thickness 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm 0.9mm 1.6mm | 0.9mm 1.6mm 1 0.9mm 1 1.6mm | 0.9mm 1.6mm | 0.9mm 1.6mm 1 0.9mm 1.6mm | 0.9mm | 1.6mm 0.9mm 1.6mm 0.9mm | 1.6mm I 0.9mm I | 1.6mm I 0.9mm I | 1.6mm Exudation test* h vS Fully involved, frosting • 53 p vB -3⁄4 V0 Main}' No change in appearance No traces observed, no change in appearance of the pattern A little spot was observed There is no change in the appearance of the pattern, there is a little exudation / - β / h XXXX &lt;&lt; 〇〇〇〇〇 &lt; XX to wetness XXXX &lt;1 〇〇〇〇〇〇XX to formulate cAPP 1 ν-ΐ 1 1 1 1 in 1 1 1 APP in IT) VO BDHPP 1 l£J 1 1 DXHPP 1 1 1 1 1 1 1 1 1 I DTHPP 1 1 1 VJ DPHPP 1 1 yn 1 1 1 BDHPP 1 1 1 1 1 1 1 1 XDHPP 1 1 1 1 1 1 1 TDHPP 1 1 1 1 IPDHPPI 1 1 1 1 1 Resin 〇ο 〇Ο 〇Ο ο 〇Ο O o 〇〇 (N tb|交例7 tbl交例8 tt4交例9 Comparative Example 10 Comparative Example 11 tt$m i2 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 π tb# 交例14 60 201209143 As a flame retardant, when using squaric acid alone and polymorphic acid, flame retardancy, properties and resistance All of the exudation (4) was not practical enough, and in particular, when the acid was used alone, it was observed that many cracks occurred in the test piece during the exudation test (Comparative Examples 5 and 6). Also, use aromatic acid - though. When strontium salt is used as a flame retardant, it is similar to the results of ammonium persalt, and the moisture resistance and age of the sputum salt are similar to those of ammonium poly-allinate, and 111 is a high wetness confirmation system. The user (Comparative Examples 1 to 4). On the other hand, when the aromatic phosphodiester piperene salt is used alone as a flame retardant, it is confirmed that high flame resistance and bleed resistance can be imparted in addition to the flame retardancy imparted to ammonium polyphosphate. Example 4). On the other hand, when a mixture of ammonium polyphosphate or coated ammonium polyphosphate and an aromatic phosphate vinegar (monoacetic acid or diacetate) is used as a flame retardant, a high degree of flame retardancy can be obtained even if a small amount is added. Examples 5 to 1 and Comparative Examples 7 to 14). However, in the case where the ammonium polyphosphate or the coated polyphosphoric acid is used together with the aromatic monophosphate piperazine salt, high flame retardancy can be imparted in any case, but it is accompanied by deterioration over time under high humidity. The appearance was poor and the flame retardancy was low (Comparative Examples 7 to 12). On the other hand, when it was confirmed that the aromatic squarish bismuth salt was used in combination with the high flame retardancy, it was able to exhibit high moisture resistance and exhibit high bleed resistance (Examples 5 to 10). However, 'when the aromatic phosphodiester piperazine was used together with the ammonium polyphosphate coating, the dispersibility of several coated ammonium polyphosphates was poor, resulting in a slight speckle pattern after the test. However, the UL94V test system after the moisture resistance test was still monthly. b is sufficient to maintain the flame retardancy of ν·〇 to V-2 (Examples 8, 8). 61 201209143 In addition, when aromatic phosphorus diester, aromatic monophosphate, and ammonium polyphosphate are used together, the high hygroscopicity of the aromatic monophosphate leads to the sulphur and Exudation was hindered (Comparative Examples 13 to 14). I: Simple description of the diagram 3 (none) [Explanation of main component symbols] (None) 62

Claims (1)

201209143 VII. Patent application scope: 1. A flame retardant composition containing a cyclic amine salt, which is a cyclic amine salt containing an aromatic acid-clear diester, and the cyclic amine salt of the aromatic phosphodiester is G is an aromatic phosphodiester of an anion component and 2) a cyclic amine which is a cationic component, wherein the cyclic amine salt is represented by the following formula (I), [Chem. 44] [wherein RcRw is the same or different from each other and represents a hydrogen atom or a hydrocarbon group which may have a substituent, and A represents that one or more imine groups (-NH-) are bonded to at least an alkyl group cyclically. The cyclic amine, Y represents an imine group, Z represents an oxygen atom, a sulfur atom or an imine group, η represents an integer of 1 to 10, ηι represents an integer of 0 to 9, and 1 represents 1 to 10 Integer]. 2. The flame retardant composition according to claim 1, wherein in the cyclic amine salt of the aromatic phosphodiester, the oxime component represented by the following formula (II) and the following formula (III) The composition ratio of the component B represented by the ion equivalent ratio is A component/B component = 0.8/1.0 to 1.0/1.2, wherein, the general formula (II): [Chem. 45] 63 201209143 R4 R5 Re R7 [wherein Ri~Rio are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; Formula (III): [Chem. 46] [In the formula, A represents a cyclic amine in which at least one imine group (-NH-) is bonded to an alkyl group to form a ring, Y represents an imine group, and Z represents an oxygen atom or sulfur. An atom or an imine group, and m represents an integer of 0 to 9]. 3. The flame retardant composition according to claim 1, wherein the content of the aromatic phosphoric acid is 1% by weight or less of the flame retardant composition. 4. A flame retardant composition according to the first aspect of the patent application, which further contains at least one of phosphates. A flame retardant resin composition containing the flame retardant composition and the resin component as in the first aspect of the patent application, wherein the resin component contains 1 to 100 parts by weight based on 100 parts by weight of the resin component. A cyclic amine salt of an aromatic phosphodiester. 6. A flame-retardant resin composition containing a flame retardant composition and a resin component as in the fourth aspect of the patent application, wherein the resin component contains 100% by weight of 201209143 parts by weight The cyclic amine salt of the aromatic phosphodiester and 1 to 50 parts by weight of the acid salt. 7. The flame-retardant resin composition according to claim 5 or 6, wherein the resin component is a polyolefin resin. A flame-retardant resin molded article obtained by molding the flame-retardant resin composition according to any one of items 5 to 7 of the above-mentioned patent application. 9_ The flame-retardant resin molded article of claim 8 is used for electrical and electronic parts, OA machine parts, home electric machine parts, automobile parts, or machine parts. 10. A method for producing a cyclic amine salt of an aromatic phosphodiester, which is a cyclic amine salt of an aromatic 4-acid diester represented by the following formula (I); Wherein R^Rio is the same or different and represents a hydrogen atom or a hydrocarbon group which may have a substituent, and A represents that at least one imine group (-NH-) is bonded to at least an alkyl group cyclically. The cyclic amine is formed, Y represents an imine group, Z represents an oxygen atom, a sulfur atom or an imine group, η represents an integer of 1 to 10, m represents an integer of 〇 9 and 1 represents 1 1 An integer of 10], the production method comprises the following steps: (1) reacting a compound represented by the following formula (IV) with a hydroxyl functional phosphorus in the presence of an amine, 65 201209143 [Chem. 48] [In the formula, Ri to R_5 are the same or different and each represents a nitrogen atom or a hydrocarbon group which may have a substituent], and a halogen-containing aromatic sulphuric acid represented by the following formula (V) is synthesized. The step of the derivative, [49] [wherein, Ri~Ri〇 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent]; (2) by hydrolyzing the element-containing aromatic acid ester derivative a step of synthesizing an aromatic phosphodiester represented by the following formula (II), [Chem. 50] [wherein, Ri to Rio are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent]; and (3) by adding the following formula (VI) to the aromatic acid diester Table 66 The compound shown in 201209143 to synthesize the compound represented by the above formula (i), [Chem. 51] [In the formula, A represents a cyclic amine in which at least one imine group (-NH-) is bonded to an alkyl group to form a ring, Y represents an imine group, and Z represents an oxygen atom or sulfur. An atom or an imine group, and m represents an integer of 0 to 9]. 67 201209143 IV. Designated representative map: . (none) (1) The representative representative of the case is: ( ) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: